US3635843A - Crystalline 1,5-diglycidylnaphthalene and cured products thereof - Google Patents
Crystalline 1,5-diglycidylnaphthalene and cured products thereof Download PDFInfo
- Publication number
- US3635843A US3635843A US842526A US3635843DA US3635843A US 3635843 A US3635843 A US 3635843A US 842526 A US842526 A US 842526A US 3635843D A US3635843D A US 3635843DA US 3635843 A US3635843 A US 3635843A
- Authority
- US
- United States
- Prior art keywords
- diglycidylnaphthalene
- crystalline
- epoxy
- anhydride
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- YQAYPSKEWNBJHH-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethyl)naphthalen-1-yl]methyl]oxirane Chemical compound C=1C=CC2=C(CC3OC3)C=CC=C2C=1CC1CO1 YQAYPSKEWNBJHH-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000004593 Epoxy Substances 0.000 claims description 22
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical group 0.000 claims description 9
- 150000008065 acid anhydrides Chemical group 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 150000007517 lewis acids Chemical group 0.000 claims description 5
- MRFOXZHVXHEJIU-UHFFFAOYSA-N 3-butyl-4-methylideneoxolane-2,5-dione Chemical compound CCCCC1C(=O)OC(=O)C1=C MRFOXZHVXHEJIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 229920000647 polyepoxide Polymers 0.000 description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 14
- 239000003822 epoxy resin Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 238000013016 damping Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- LHIWDXPDEOCBIG-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethyl)naphthalen-2-yl]methyl]oxirane Chemical compound C=1C=C2C=CC=CC2=C(CC2OC2)C=1CC1CO1 LHIWDXPDEOCBIG-UHFFFAOYSA-N 0.000 description 7
- -1 diallyl naphthalenes Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ACZFBYCNAVEFLC-YFKPBYRVSA-N (S)-3-(imidazol-5-yl)lactic acid Chemical compound OC(=O)[C@@H](O)CC1=CN=CN1 ACZFBYCNAVEFLC-YFKPBYRVSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- TXVWTOBHDDIASC-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)=C(N)C1=CC=CC=C1 TXVWTOBHDDIASC-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- OFGDSGVGRWPQJQ-UHFFFAOYSA-N 1h-imidazol-1-ium;acetate Chemical compound CC(O)=O.C1=CNC=N1 OFGDSGVGRWPQJQ-UHFFFAOYSA-N 0.000 description 1
- WMDREPIZMRNXAT-UHFFFAOYSA-N 1h-imidazole;phthalic acid Chemical compound C1=CNC=N1.OC(=O)C1=CC=CC=C1C(O)=O WMDREPIZMRNXAT-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- CIPOCPJRYUFXLL-UHFFFAOYSA-N 2,3,4-tris[(dimethylamino)methyl]phenol Chemical class CN(C)CC1=CC=C(O)C(CN(C)C)=C1CN(C)C CIPOCPJRYUFXLL-UHFFFAOYSA-N 0.000 description 1
- DEWOCTXUQBMPCX-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;1h-imidazole Chemical compound C1=CNC=N1.OC(=O)C(O)C(O)C(O)=O DEWOCTXUQBMPCX-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- PFJPHQUZCRACDD-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=C(CC2OC2)C=CC=1CC1CO1 PFJPHQUZCRACDD-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- IOCXBXZBNOYTLQ-UHFFFAOYSA-N 3-nitrobenzene-1,2-diamine Chemical compound NC1=CC=CC([N+]([O-])=O)=C1N IOCXBXZBNOYTLQ-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KAMGOKSXKBHPHL-UHFFFAOYSA-N benzene-1,2,3,4-tetramine Chemical compound NC1=CC=C(N)C(N)=C1N KAMGOKSXKBHPHL-UHFFFAOYSA-N 0.000 description 1
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- RKYSWCFUYJGIQA-UHFFFAOYSA-H copper(ii) arsenate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RKYSWCFUYJGIQA-UHFFFAOYSA-H 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- KNRCVAANTQNTPT-UHFFFAOYSA-N methyl-5-norbornene-2,3-dicarboxylic anhydride Chemical compound O=C1OC(=O)C2C1C1(C)C=CC2C1 KNRCVAANTQNTPT-UHFFFAOYSA-N 0.000 description 1
- UVDIQZVDGVRRLR-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].[Na].C1=CC=CC2=CC=CC=C21 UVDIQZVDGVRRLR-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
Definitions
- PATENTED JAN. 8 1912 PHENYLENED cou'moL Erxf liE'siu' 'A/ AIINF CONTROL-EPOXY B/m PHENYLEIEDIAIINE -Nu4ub lxvmoaoommo 1 's-0cm WEIGHT LOSS HOURS AT 500F(
- the present invention is directed to crystalline l,5- diglycidylnaphthalene and to the preparation thereof.
- the present invention is further directed to cured compositions of crystalline l,5-diglycidylnaphthalene with an epoxy curing agent, particularly amines and more particularly metaphenylenediamine.
- FIG. 1 is a graph of the thermal stability of epoxy resin castings cured with various epoxy curing agents measured by percent weight loss as a function of time at 500 F.
- FIG. 2 is a graph of the effect of high-temperature exposure on elastic modulus versus test temperature for l,5-diglycidylnaphthalene/m-phenylenediamine castings.
- FIG. 3 is a graph of the effect of heat exposure on damping characteristics of the l,5-DGN/metaphenylenediamine castings.
- the present invention is particularly directed to crystalline l,5diglycidylnaphthalene and to the cured compositions thereof with epoxy curing agents, particularly metaphenylenediamine.
- l,5-diglycidylnaphthalene is prepared in a straightforward manner using known techniques, reactants, and reaction conditions.
- Diallylnaphthalene is first prepared by conventional methods wherein naphthalene is reacted with allyl chloride in the presence of Friedel-Crafts catalysts such as FeCl AlCl or ZnCl
- the resulting product is, of course, a mixture of mono-, di and tri-allylnaphthalenes.
- the allylnaphthalenes are then separated by conventional distillation techniques and further refined to give a fraction rich in the l,5-isomer.
- allylic-substituted naphthalenes may be prepared by reacting disodium naphthalene with allyl chloride and that other methods for making the diallyl naphthalenes will be apparent to those skilled in the art.
- the epoxidation of the allyl radicals attached to the naphthalene ring may be advantageously carried out by reacting the allylnaphthalene with an epoxidizing agent.
- Organic peracids such as peracetic acid, perbenzoic acid, monoperphthalic acid and the like, are preferred agents for epoxidation.
- the amount of the epoxidizing agent employed will vary over a considerable range; however, in general, one employs at least one mole of the epoxidizing agent to every ethylenic group to be epoxidized. Thus, to produce l,5-c1iglycidylnaphthalene, one would react 1 mole of 1,5-diallylnaphthalene with approximately 2 moles of the epoxidizing agent.
- Chloroform is an especially useful solvent, but other solvents include ethyl ether, dichloroethane, benzene, ethyl acetate, and the like. It is not necessary to operate under anhydrous conditions, but the amount of water present should be limited so as to avoid excessive hydrolysis of the epoxy groupsv Up to about 25 percent water may be tolerated in the reaction mixture.
- the temperature employed during the epoxidation may vary over a considerable range depending upon the epoxidizing agent selected. It is generally desirable to maintain the temperature between -20 and C., and more preferably between 10 and 60 C. Atmospheric, subatmospheric or superatmospheric pressures may be employed as desired.
- the resulting 1,S-digIycidyInaphthalene may then be recovered from the reaction mixture by any means known in the art, such as distillation, extraction, filtration, fractional precipitation and the like as well as combinations of techniques.
- 1,5-digylcidylnaphthalene prepared as described herein is a crystalline solid having a melting point of 124 C. and a weight per epoxy (WPE) value essential equal to the theoretical value of 120.
- WPE weight per epoxy
- the naphthalene, allyl chloride, hexane, and CaCO; were charged to the flask with stirring.
- the reaction mixture was then slurried with filter aid and filtered through a Buchner funnel. The solids on the filter were washed with 3X250 ml.
- the reaction mixture composition was as follows:
- reaction mixture was transferred to a separatory funnel and allowed to phase.
- the upper aqueous phase was removed, and discarded.
- the lower organic phase was washed with 2x350 ml. percent wt. aqueous NaCl solution, l l50 ml. 10 percent wt. aqueous Na CO solution, and finally with 1X350 ml. 10 percent wt. aqueous NaCl solution.
- the lower organic phase was then slurried with filter aid and anhydrous Na SO and after minutes was filtered through a Buchner funnel. Volatiles were stripped from the filtrate to terminal conditions of 1 10 C. and 80 mm. Hg pressure. The residual resin amounted to 72 grams and had WPE value of 15 l.
- This mixed diallylnaphthalene was epoxidized as before to the corresponding mixture of diglycidylnaphthalenes.
- the product had a WPE of [57, which is substantially the same as that of the corresponding liquid product discussed in the preceding section (prepared from a diallylnaphthalene cut rich in the l,5-isomer). It was not possible to induce crystallization in the mixed diglycidylnaphthalene isomers.
- the crystalline l,S-diglycidylnaphthalene may be cured through the epoxy groups to form valuable polymeric products having outstanding physical properties, particularly thermal stability.
- the crystalline l,S-diglycidylnaphthalene may he polymerized alone or with other polyepoxide material in a variety ofdifferent proportions, such as, for example, with amounts of other epoxides varying from 5 percent to 95 percent by weight.
- Crystalline l,S-diglycidylnaphthalene can be cured with conventional epoxy resins curing agents such as acids, acid anhydrides, amines, polyamines, Friedel'Crafts compounds, Lewis acids, imidazoles compounds and salts, and the like to form hard, insoluble, infusible products having excellent high temperature properties.
- epoxy resins curing agents such as acids, acid anhydrides, amines, polyamines, Friedel'Crafts compounds, Lewis acids, imidazoles compounds and salts, and the like to form hard, insoluble, infusible products having excellent high temperature properties.
- Curing agents that can be utilized include, among others, amines, amino-containing polymers, polybasic acids, acid anhydrides, salts, mercaptans, hydrazines, BF -complexes, and the like, and mixtures thereof.
- Such material include, among others, p-phenylene diamine, diaminodiphenylsulfone, p,p-methylene dianiline, p,pdiaminophenylmethane, triaminobenzene, 2,4- diaminotoluene, tetraaminobenzene, 3,3-diamino diphenyl, l,3-diamino-4-isopropylbenzene, l,3-diamino-4,5-diethylbenzene, diaminostilbene, triethylamine, ethylene diamine, diethylamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pyridine, diaminopyridine, piperidine, N,N-diethyl-l,3-propanediamine, dicyandiamide, melamine, fatty acid salts of amines, such as the 2-ethylhe
- acid anhydrides such as phthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, hexachlorophthalic anhydride, Nadic anhydride [endo-cis-bicyclo(2.2.
- Still other examples include the salts, such as magnesium perchlorate, zinc fluoborate, potassium persulfate, copper fluoborate, cupric arsenate, zinc persulfate, cupric fluosilicate, cupric iodate, cupric sulfate, magnesium nitrate, magnesium phosphate, stannic fluoborate, zinc nitrate, and the like, as well as the chloride and the like.
- the salts such as magnesium perchlorate, zinc fluoborate, potassium persulfate, copper fluoborate, cupric arsenate, zinc persulfate, cupric fluosilicate, cupric iodate, cupric sulfate, magnesium nitrate, magnesium phosphate, stannic fluoborate, zinc nitrate, and the like, as well as the chloride and the like.
- Still other examples include the BF adducts and complexes with various materials, such as amines, amides, ethers, phenols, alcohols, water and the like.
- Very suitable BF adducts are the BF etherates such as BF 3 ethylamine complex, BF phenolates, BF -hydrates and BF alcoholates.
- catalysts include 3-aminopyridine and the imidazole compounds and their salts, such as, for example, 2-methyl-4- ethyl imidazole, imidazole, benzimidazole, imidazole lactate,
- the amount of the curing agents employed will also vary over a wide range.
- the amount of the curing agents having active hydrogen as well as the agents such as acid anhydrides are preferably employed so as to furnish at least 0.6 equivalents and still more preferably 0.8 to 1.5 equivalent per equivalent of the polyepoxide.
- equivalent means that amount needed to furnish one active hydrogen or anhydride group per epoxy group.
- the other curing agents, such as metal salts, tertiary amines, BF and the like are preferably used in amounts varying from about 0.] percent to 6 percent by weight of the 1,5- diglycidylnaphthalene.
- Particularly outstanding cured products having excellent high temperature properties are prepared when the curing agent is metaphenylenediamine.
- compositions of crystalline l,5- diglycidylnaphthalene and metaphenylenediamine exhibit a thermal stability greater than theretofore known for epoxy compositions and are therefore extremely valuable for high temperature metal to metal adhesives. It has further unexpectedly been found that the 1,5-isomer has a thermal stability much greater than that of the mixed isomers.
- EXAMPLE I This example illustrates the improved elevated temperature properties of l,S-digIycidyInaphthalene (1,5-DGN) cured with metaphenylenediamine over conventional epoxy resins or the mixed isomer of DGN.
- the stoichometric amount of molten metaphenylenediamine was dissolved in (I) molten l,5-diglycidylnaphthalene (LS-DON), (2) mixed isomers of diglycidylnaphthalene, (3) Epoxy Resin A, and (4) Epoxy Resin B. Small discs were cast of each system, allowed to gel overnight at room temperature, and cured for 4 hours at 100 C. plus 4 hours at 200 C. Similar castings were made with l,5-DGN cured with l the stoichometric amount of Nadic methyl anhydride (NMA) plus 0.2 percent wt. (of total) of benzyldimethylamine, and 2) 2 percent boron trifloride ethylamine complex (BF- 400). These two castings were also cured for 4 hours at l00 C. plus 4 hours at 200 C.
- NMA Nadic methyl anhydride
- BF- 400 2 percent boron trifloride ethy
- a torsion pendulum rod of 1,5-DGN cured with metaphenylenediamine was prepared as in example I and subjected to exposure in a forced draft oven at 500 F. At appropriate intervals the specimen was removed and the shear modulus and damping factor determined over the temperature range of 23-240bL C.
- FIGS. 2 and 3 present the data obtained after three exposure times, viz, zero, 1,000, and 2,000 hours (intermediate data has been omitted to simplify the figures).
- FIG. 2 gives the varia' tion of the elastic component, G, of the complex shear modulus with temperature.
- G the elastic component of the complex shear modulus with temperature.
- FIG. 3 shows the effect of exposure on the damping characteristics (a measure of the plastic component of the complex shear modulus) of the system.
- the damping characteristics a measure of the plastic component of the complex shear modulus
- the shift of the damping peak indicative of the second order transition temperature, from about 250 C. initially to a temperature considerably beyond 260 C.
- the generally low level of damping indicating a predominantly elastic material.
- E 2G'( I+i1.)
- a typical value of a glassy polymer the data of FIG. 2 can be conveniently recast to show the effect of 500 F. exposure on the Youngs modulus at room temperature and 200 C.
- a cured composition exhibiting high glass transition temperatures and high thermal stability comprising the reaction product of crystalline l,SdigIycidyInaphthaIene and a curing amount of an epoxy curing agent.
- composition as in claim I wherein the epoxy curing agent is an amine.
- composition as in claim 3 wherein the amine is metaphenylenediamine.
- composition as in claim 1 wherein the epoxy curing agent is an acid anhydride.
- composition as in claim 5 wherein the anhydride is methyl [2.2.1 heptene-2,3-dicarboxylic anhydride.
- composition as in claim 1 wherein the epoxy curing agent is a Lewis acid.
- composition as in claim 7 wherein the Lewis acid is a BF complex.
Abstract
The preparation of crystalline 1,5-diglycidylnaphthalene is described. The present invention is further directed to curable and cured compositions of 1,5-diglycidylnaphthalene.
Description
United States Patent Parry et al.
[ CRYSTALLINE 1,5-
DIGLYCIDYLNAPHTHALENE AND CURED PRODUCTS THEREOF [72] Inventors: Harvey L. Parry, Summit; Alton J. Landua, Maplewood, both of NJ.
[73] Assignee: Shell Oil Company, New York, NY. 221 Filed: July 17, 1 969 [2]] Appl. No.: 842,526
[52] U.S.Cl ..260/2N,117/127,1l7/l6lZB, 161/186, 260/2 EC, 260/2 A, 260/78.4 EP [51] Int. Cl ..C08g 23/20 [58] Field of Search ..260/348, 2 EP, 2 A, 2 EC, 78.4 EP
m 0 (ml Im- PHEIIYLENEDIAIIN WEIGHT LOSS m N N u as c a on N 7 [151 3,635,843 [4 1 Jan. 18, 1972 [56] References Cited UNITED STATES PATENTS 2,938,875 5/1960 Martin et al. ..260/348 X Primary Examiner-William H. Short Assistant Examiner-T. Pertilla Attorney-Joseph W. Brown and Norris E. Faringer [57] ABSTRACT The preparation of crystalline 1,5-diglycidylnaphthalene is described. The present invention is further directed to curable and cured compositions of l,S-diglycidylnaphthalene.
8 Claims, 3 Drawing Figures CONTROL-EPOXY B/ n PHENYLENEDIAIINE I 1 5 -0Gll/NIA m P NY EDIMIIN HOURS AT 500'F(IN AIR) THERMAL STABILITY OF EPOXY RESIN CASTINGS e, PSI
PATENTED JAN. 8 1912 PHENYLENED cou'moL Erxf liE'siu' 'A/ AIINF CONTROL-EPOXY B/m PHENYLEIEDIAIINE -Nu4ub lxvmoaoommo 1 's-0cm WEIGHT LOSS HOURS AT 500F(|N MR) THERMAL STABILITY OF EPOXY RESIN CASTINGS FIG.
DAMPING, LOG DECREMENT TEST TEIPERATURE,C EFFECT OF 500F EXPOSURE 0N DAHPING VS. TEST TEIPERATURE FOR I, 5- DGN/m- PHENYLENEDIAMINE CASTINGS FIG. 3
TEST TEMPERATURE") EFFECT OF 500F EXPOSURE 0N ELASTIC uoouws vs TEST TEMPERATURE FOR l,5,-D6N/ n PHENYLENEDIAMINE CASTINGS FIG. 2
THEIE? ATTORNEY CRYSTALLINE 1,S-DIGLYCIDYLNAPHTHALENE AND CURED PRODUCTS THEREOF BACKGROUND OF THE INVENTION The preparation of polysubstituted aromatic compounds such as the poly (vic-epoxyalkyl) benzenes, e.g., 1,4-bis (2,3- epoxypropyl) benzene is known. It is also known to epoxidize ethylenically unsaturated aromatic hydrocarbons such as the diallyl naphthalenes to form the glycidyl derivatives thereof. See, for example, U.S. Pat. No. 2,938,875. The preparation described in U.S. Pat. No. 2,938,875 as well as in other prior sources have produced crude mixtures of unascertained isomers and the like containing principally the 1,2- and 1,3- isomers. Thus, it has not heretofore been possible to prepare pure, crystalline I,5-diglycidylnaphthalene.
SUMMARY OF THE INVENTION The present invention is directed to crystalline l,5- diglycidylnaphthalene and to the preparation thereof. The present invention is further directed to cured compositions of crystalline l,5-diglycidylnaphthalene with an epoxy curing agent, particularly amines and more particularly metaphenylenediamine.
It was discovered quite unexpectedly that when crystalline l,S-diglycidylnaphthalene is cured with epoxy curing agents, the resulting cured products are polymers exhibiting a high Tg (i.e., glass transition temperature as indicated by rapid increase in vibrational damping of the specimen in a torsion pendulum test as the test temperature is increased) and excellent thermal stability. When the curing agent is metaphenylenediamine, the resulting product has outstandingly improved thermal stability over conventional epoxy resin systems or over mixed diglycidylnaphthalene isomers.
BRIEF DESCRIPTION OF THE DRAWINGS In the drawings:
FIG. 1 is a graph of the thermal stability of epoxy resin castings cured with various epoxy curing agents measured by percent weight loss as a function of time at 500 F.
FIG. 2 is a graph of the effect of high-temperature exposure on elastic modulus versus test temperature for l,5-diglycidylnaphthalene/m-phenylenediamine castings.
FIG. 3 is a graph of the effect of heat exposure on damping characteristics of the l,5-DGN/metaphenylenediamine castings.
DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention is particularly directed to crystalline l,5diglycidylnaphthalene and to the cured compositions thereof with epoxy curing agents, particularly metaphenylenediamine.
Briefly, l,5-diglycidylnaphthalene is prepared in a straightforward manner using known techniques, reactants, and reaction conditions. Diallylnaphthalene is first prepared by conventional methods wherein naphthalene is reacted with allyl chloride in the presence of Friedel-Crafts catalysts such as FeCl AlCl or ZnCl The resulting product is, of course, a mixture of mono-, di and tri-allylnaphthalenes. The allylnaphthalenes are then separated by conventional distillation techniques and further refined to give a fraction rich in the l,5-isomer.
It will be appreciated that the allylic-substituted naphthalenes may be prepared by reacting disodium naphthalene with allyl chloride and that other methods for making the diallyl naphthalenes will be apparent to those skilled in the art.
The epoxidation of the allyl radicals attached to the naphthalene ring may be advantageously carried out by reacting the allylnaphthalene with an epoxidizing agent. Organic peracids, such as peracetic acid, perbenzoic acid, monoperphthalic acid and the like, are preferred agents for epoxidation.
The amount of the epoxidizing agent employed will vary over a considerable range; however, in general, one employs at least one mole of the epoxidizing agent to every ethylenic group to be epoxidized. Thus, to produce l,5-c1iglycidylnaphthalene, one would react 1 mole of 1,5-diallylnaphthalene with approximately 2 moles of the epoxidizing agent.
It is preferred to carry out the epoxidation reaction in a suitable mutual solvent for the reactants and product. Chloroform is an especially useful solvent, but other solvents include ethyl ether, dichloroethane, benzene, ethyl acetate, and the like. It is not necessary to operate under anhydrous conditions, but the amount of water present should be limited so as to avoid excessive hydrolysis of the epoxy groupsv Up to about 25 percent water may be tolerated in the reaction mixture.
The temperature employed during the epoxidation may vary over a considerable range depending upon the epoxidizing agent selected. It is generally desirable to maintain the temperature between -20 and C., and more preferably between 10 and 60 C. Atmospheric, subatmospheric or superatmospheric pressures may be employed as desired.
The resulting 1,S-digIycidyInaphthalene may then be recovered from the reaction mixture by any means known in the art, such as distillation, extraction, filtration, fractional precipitation and the like as well as combinations of techniques.
1,5-digylcidylnaphthalene prepared as described herein is a crystalline solid having a melting point of 124 C. and a weight per epoxy (WPE) value essential equal to the theoretical value of 120.
Synthesis of Crystalline l,S-diglycidylnaphthalene A. Preparation of l,5-diallylnaphthalene The equipment consisted of a 5-liter, four-necked, round bottom, flask fitted with a stirrer, reflux condenser and thermometer.
The charge to the reaction flask was as follows:
Moles Grams ml.
Naphthalene 4 512 Ally] Chloride l7.6 L346 Hcxane 1,440 CaCO;, s 800 F BC I 0.2 32
The naphthalene, allyl chloride, hexane, and CaCO; were charged to the flask with stirring. The temperature dropped from ambient (25 C.) to 12 C. because of the negative heat of solution of naphthalene in allyl chloride. The FeCl was then added with vigorous stirring whereupon the temperature rose from 12 to 25 C. in one-half hour. The temperature was then taken to reflux over a period of about three-quarters of an hour and vigorous reflux was maintained for an additional 4 hours. The reaction mixture was then slurried with filter aid and filtered through a Buchner funnel. The solids on the filter were washed with 3X250 ml. of hexane, and the combined filtrates washed successively with 2X1,000 ml. distilled water, lXl,000 ml. l0 percent wt. aqueous Na CO and finally lX1,000 ml. distilled water, the organic phase always being the upper one.
The excess allyl chloride and hexane were stripped from the organic phase at atmospheric pressure, and unreacted naphthalene (285.4 grams, 48.5 percent wt.) to final conditions of 94 C. kettle temperature and 0.1 mm. Hg pressure. A midcut consisting of mixed monoand di-allylnaphthalenes (269.8 grams, 46.0 percent wt.) was then taken to 190 C. and 0.1 mm. Hg pressure. Rejected bottoms amounted to 32.5 grams, or 5.5 percent wt. of the volatiles-free crude reaction mixture.
The midcut from the above distillation was then fractionated with a 20-plate Oldershaw distillation column and associated equipment. Using a 2/1 reflux ratio, and 0.l mm. Hg pressure diallylnaphthalene cut was taken in the boiling range of l28-143 C., vapor temperature, and amounted to 84.2
grams. Spectroscopic analysis indicated this particular cut contained greater than 50 percent ofthe 1,5-isomer.
B. Preparation of Crystalline l,S-digIycidylnaphthalene The equipment consisted of a l-liter, four-necked, roundbottomed, flask fitted with a stirrer, reflux condenser, thermosmeter, and graduated dropping funnel. The flask was immersed in a thermostatically controller water bath.
The reaction mixture composition was as follows:
Chemical Grams Equivalents Mls Diallylnaphthalene 78 0.75 78 Cut CHCL 288 194 40.0% Pcraeetic 2l4 L125 Acid NaC,H,O,-3H,O 6 0.0437 202 H l2 Total 598 474 The diallylnaphthalene and CHCl were charged to the flask, and equilibrated at 46 C. While this was taking place the NaC H O -3H O in the indicated amount of water was added to the 40 percent peracetic acid. This solution was then placed in the dropping funnel, and added to the reaction mixture over a period of 39 minutes, the temperature during this period being controlled to 50 i C., by the rate of addition, and by adjustment of the bath temperature. The temperature of the reaction mixture was then controlled at SOL-1 C. for an additional I66 minutes.
After cooling to about 30 C., the reaction mixture was transferred to a separatory funnel and allowed to phase. The upper aqueous phase was removed, and discarded. The lower organic phase was washed with 2x350 ml. percent wt. aqueous NaCl solution, l l50 ml. 10 percent wt. aqueous Na CO solution, and finally with 1X350 ml. 10 percent wt. aqueous NaCl solution.
The lower organic phase was then slurried with filter aid and anhydrous Na SO and after minutes was filtered through a Buchner funnel. Volatiles were stripped from the filtrate to terminal conditions of 1 10 C. and 80 mm. Hg pressure. The residual resin amounted to 72 grams and had WPE value of 15 l.
A portion of this product grams) was dissolved in 100 ml. CH ',OH, and the solution allowed to stand in the refrigerator (5-l0 C.) overnight. 4.4 grams of crystals were recovered which after devolatilization had a melting point of l20l 22 C. and a WPE value of 122. After recrystallization from 40 volumes of CH OH, the melting point was 124 C., and the weight per epoxy was 121. The formula weight WPE value for a pure diglycidylnaphthalene is 120. The infrared scan and NMR spectrum corresponded to those of a l,5-dis ubstituted naphthalene. A GPC scan showed only one component, the l,5-diglycidylnaphthalene.
The reaction of naphthalene with allyl chloride as given above was repeated but in this case the midcut from the first distillation was not further refined. Spectroscopic analysis indicated that the material was a mixture of l ,2-, 1,4- and l,5-diallylnaphthalene with the l,5-isomer constituting of less than 50 percent.
This mixed diallylnaphthalene was epoxidized as before to the corresponding mixture of diglycidylnaphthalenes. The product had a WPE of [57, which is substantially the same as that of the corresponding liquid product discussed in the preceding section (prepared from a diallylnaphthalene cut rich in the l,5-isomer). It was not possible to induce crystallization in the mixed diglycidylnaphthalene isomers.
The crystalline l,S-diglycidylnaphthalene may be cured through the epoxy groups to form valuable polymeric products having outstanding physical properties, particularly thermal stability. The crystalline l,S-diglycidylnaphthalene may he polymerized alone or with other polyepoxide material in a variety ofdifferent proportions, such as, for example, with amounts of other epoxides varying from 5 percent to 95 percent by weight.
Crystalline l,S-diglycidylnaphthalene can be cured with conventional epoxy resins curing agents such as acids, acid anhydrides, amines, polyamines, Friedel'Crafts compounds, Lewis acids, imidazoles compounds and salts, and the like to form hard, insoluble, infusible products having excellent high temperature properties.
Curing agents that can be utilized include, among others, amines, amino-containing polymers, polybasic acids, acid anhydrides, salts, mercaptans, hydrazines, BF -complexes, and the like, and mixtures thereof. Specific examples of such material include, among others, p-phenylene diamine, diaminodiphenylsulfone, p,p-methylene dianiline, p,pdiaminophenylmethane, triaminobenzene, 2,4- diaminotoluene, tetraaminobenzene, 3,3-diamino diphenyl, l,3-diamino-4-isopropylbenzene, l,3-diamino-4,5-diethylbenzene, diaminostilbene, triethylamine, ethylene diamine, diethylamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pyridine, diaminopyridine, piperidine, N,N-diethyl-l,3-propanediamine, dicyandiamide, melamine, fatty acid salts of amines, such as the 2-ethylhexoate of tris (dimethylaminomethyl) phenol adducts of polyepoxides such as those described hereinafter, and the above-described monoand polyamines, as the adduct of pphenylene diamine and styrene oxide, the adduct of p-phenylene diamine and allyl glycidyl ether, the adduct of diglycidylether of 2,2-bis(4-hydroxyphenyl)propane and diethylene triamine, the adducts of diethylene triamine and ethylene oxide, the adduct of diethylene triamine and styrene oxide, the adducts of polyamines and unsaturated nitriles, such as the adduct of diethylene triamine and acrylonitrile, the adduct of diethylene triamine and unsaturated sulfolanes, and the adduct of p-phenylene diamine and acrylonitrile,
Other examples include the amino-containing polyamides as described in US. Pat. No. 2,450,940 and the monomeric amides described in US. Pat. No. 2,832,799.
Other examples include the acid anhydrides such as phthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, hexachlorophthalic anhydride, Nadic anhydride [endo-cis-bicyclo(2.2. l )-5-heptene-2,3-heptene- 2,3-dicarboxylic anhydride], methyl Nadic anhydride [methylbicyclo (2.2.1)-heptene-2,3-dicarboxylic anhydride], anhydrides obtained by reacting maleic anhydride with unsaturated compounds, such as oils, terpinene, long chain unsaturated acids and the like as well as anhydrides obtained by reacting long chain acids with acetic anhydride and the like.
Still other examples include the salts, such as magnesium perchlorate, zinc fluoborate, potassium persulfate, copper fluoborate, cupric arsenate, zinc persulfate, cupric fluosilicate, cupric iodate, cupric sulfate, magnesium nitrate, magnesium phosphate, stannic fluoborate, zinc nitrate, and the like, as well as the chloride and the like.
Still other examples include the BF adducts and complexes with various materials, such as amines, amides, ethers, phenols, alcohols, water and the like. Very suitable BF adducts are the BF etherates such as BF 3 ethylamine complex, BF phenolates, BF -hydrates and BF alcoholates.
Other catalysts include 3-aminopyridine and the imidazole compounds and their salts, such as, for example, 2-methyl-4- ethyl imidazole, imidazole, benzimidazole, imidazole lactate,
imidazole acetate, imidazole tartrate, imidazole phthalate and the like.
The amount of the curing agents employed will also vary over a wide range. The amount of the curing agents having active hydrogen as well as the agents such as acid anhydrides are preferably employed so as to furnish at least 0.6 equivalents and still more preferably 0.8 to 1.5 equivalent per equivalent of the polyepoxide. As used herein in relation to the amount of curing agent, equivalent means that amount needed to furnish one active hydrogen or anhydride group per epoxy group. The other curing agents, such as metal salts, tertiary amines, BF and the like are preferably used in amounts varying from about 0.] percent to 6 percent by weight of the 1,5- diglycidylnaphthalene.
Particularly outstanding cured products having excellent high temperature properties are prepared when the curing agent is metaphenylenediamine.
It has been found that compositions of crystalline l,5- diglycidylnaphthalene and metaphenylenediamine exhibit a thermal stability greater than theretofore known for epoxy compositions and are therefore extremely valuable for high temperature metal to metal adhesives. It has further unexpectedly been found that the 1,5-isomer has a thermal stability much greater than that of the mixed isomers.
The following examples are presented in order to illustrate the cured compositions of the present invention. Unless otherwise specified parts are given by weight.
EXAMPLE I This example illustrates the improved elevated temperature properties of l,S-digIycidyInaphthalene (1,5-DGN) cured with metaphenylenediamine over conventional epoxy resins or the mixed isomer of DGN.
The stoichometric amount of molten metaphenylenediamine was dissolved in l molten 1,5-DGN, (2) mixed isomers of DGN, (3) Epoxy Resin A [a glycidyl polyether of 2,2-bis(4-hydroxyphenyl)propane having an average molecular weight of approximately 360 and an epoxide equivalent weight of I88], and (4) Epoxy Resin B [a glycidyl ether of a phenol-novolac resin]. Rod coatings one-eighth inch diameter by four inch long were made using a cure cycle of 1 hour at 100 C. plus 1 hour at 200 C. The glass transition temperature (Tg) of these castings was determined (via torsion pendulum damping versus test temperature) to be as follows:
Mixed Resin Epoxy Epoxy Isomers l,5 Property Resin A Resin B of DGN -DGN WPE (weight per epoxide) I88 I77 I57 I20 Molecule Weight 360 620 300 240 Epoxies per Mole L9 3.5 L9 2.0 Tg, C., of
Cured Casting I65 240 205 250 EXAMPLE II This example illustrates the improved thermal stability of l,S-diglycidylnaphthalene over the mixed isomers of diglycidylnaphthalene and over conventional epoxy resins.
The stoichometric amount of molten metaphenylenediamine was dissolved in (I) molten l,5-diglycidylnaphthalene (LS-DON), (2) mixed isomers of diglycidylnaphthalene, (3) Epoxy Resin A, and (4) Epoxy Resin B. Small discs were cast of each system, allowed to gel overnight at room temperature, and cured for 4 hours at 100 C. plus 4 hours at 200 C. Similar castings were made with l,5-DGN cured with l the stoichometric amount of Nadic methyl anhydride (NMA) plus 0.2 percent wt. (of total) of benzyldimethylamine, and 2) 2 percent boron trifloride ethylamine complex (BF- 400). These two castings were also cured for 4 hours at l00 C. plus 4 hours at 200 C.
All of the above castings were weighed and placed in a forced draft oven operating at 500 F. At appropriate intervals the casings were removed from the oven, cooled, weighed and returned to the oven. The resulting data are graphically presented in FIG. I and clearly show the superior thermal stability of 1,5-DGN.
EXAMPLE III This example further illustrates the thermal stability of 1,5- DGN.
A torsion pendulum rod of 1,5-DGN cured with metaphenylenediamine was prepared as in example I and subjected to exposure in a forced draft oven at 500 F. At appropriate intervals the specimen was removed and the shear modulus and damping factor determined over the temperature range of 23-240bL C.
The shear modulus characteristics of the m-phenylenediamine-cured castings were analyzed via torsion pendulum tests at several intervals during the 500 F. exposure. FIGS. 2 and 3 present the data obtained after three exposure times, viz, zero, 1,000, and 2,000 hours (intermediate data has been omitted to simplify the figures). FIG. 2 gives the varia' tion of the elastic component, G, of the complex shear modulus with temperature. The difi'erence between the three curves, while considered experimentally valid, are small; perhaps of greater significance is the absence of signs of embrittlement (increase of room temperature modulus) during exposure.
FIG. 3 shows the effect of exposure on the damping characteristics (a measure of the plastic component of the complex shear modulus) of the system. Of significance here is the shift of the damping peak, indicative of the second order transition temperature, from about 250 C. initially to a temperature considerably beyond 260 C. Also of significance is the generally low level of damping, indicating a predominantly elastic material.
For a predominantly elastic material Young's modulus can be calculated from torsion pendulum data by the equation E=2G'( I+i1.) By assuming a Poissons Ratio (;1.) of 0.35, a typical value of a glassy polymer the data of FIG. 2 can be conveniently recast to show the effect of 500 F. exposure on the Youngs modulus at room temperature and 200 C.
We claim as our invention: 1. A cured composition exhibiting high glass transition temperatures and high thermal stability comprising the reaction product of crystalline l,SdigIycidyInaphthaIene and a curing amount of an epoxy curing agent.
2. A composition as in claim I wherein the epoxy curing agent is employed in an approximately stoichiometrical amount.
3. A composition as in claim I wherein the epoxy curing agent is an amine.
4. A composition as in claim 3 wherein the amine is metaphenylenediamine.
5. A composition as in claim 1 wherein the epoxy curing agent is an acid anhydride.
6. A composition as in claim 5 wherein the anhydride is methyl [2.2.1 heptene-2,3-dicarboxylic anhydride.
7. A composition as in claim 1 wherein the epoxy curing agent is a Lewis acid.
8. A composition as in claim 7 wherein the Lewis acid is a BF complex.
Claims (7)
- 2. A composition as in claim 1 wherein the epoxy curing agent is employed in an approximately stoichiometrical amount.
- 3. A composition as in claim 1 wherein the epoxy curing agent is an aminE.
- 4. A composition as in claim 3 wherein the amine is metaphenylenediamine.
- 5. A composition as in claim 1 wherein the epoxy curing agent is an acid anhydride.
- 6. A composition as in claim 5 wherein the anhydride is methyl (2.2.1) heptene-2,3-dicarboxylic anhydride.
- 7. A composition as in claim 1 wherein the epoxy curing agent is a Lewis acid.
- 8. A composition as in claim 7 wherein the Lewis acid is a BF3 complex.
Applications Claiming Priority (1)
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US84252669A | 1969-07-17 | 1969-07-17 |
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US3635843A true US3635843A (en) | 1972-01-18 |
Family
ID=25287538
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US842526A Expired - Lifetime US3635843A (en) | 1969-07-17 | 1969-07-17 | Crystalline 1,5-diglycidylnaphthalene and cured products thereof |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0018950A1 (en) * | 1979-05-08 | 1980-11-12 | Ciba-Geigy Ag | Crystalline epoxy resin based one component systems and their application |
US4687832A (en) * | 1984-09-20 | 1987-08-18 | Dainippon Ink And Chemicals, Inc. | Novel epoxy resin compositions |
US4707534A (en) * | 1986-12-09 | 1987-11-17 | Minnesota Mining And Manufacturing Company | Glycidylethers of fluorene-containing bisphenols |
US4786668A (en) * | 1986-06-09 | 1988-11-22 | Shell Oil Company | Resin materials |
US4786669A (en) * | 1986-06-09 | 1988-11-22 | Shell Oil Company | Lightly cross-linked resin materials |
EP0428871A2 (en) * | 1989-11-22 | 1991-05-29 | Sumitomo Bakelite Company Limited | Epoxy resin composition for semiconductor sealing |
EP0450944A2 (en) * | 1990-04-04 | 1991-10-09 | Toray Industries, Inc. | An epoxy resin composition for encapsulating a semiconductor device |
WO1996018669A1 (en) * | 1994-12-16 | 1996-06-20 | Ppg Industries, Inc. | Epoxy-amine barrier coatings with aryloxy or aryloate groups |
EP0878471A1 (en) * | 1997-05-16 | 1998-11-18 | National Starch and Chemical Investment Holding Corporation | Reactive radiation- or thermally-initiated cationically-curable epoxide monomers and compositions made from those monomers |
EP0878472A1 (en) * | 1997-05-16 | 1998-11-18 | National Starch and Chemical Investment Holding Corporation | Reactive radiation- or thermally- initiated cationically-curable epoxide monomers and compositions made from those monomers |
US5939472A (en) * | 1994-03-04 | 1999-08-17 | Mitsubishi Denki Kabushiki Kaisha | Epoxy resin composition for molding having improved mechanical properties and crack resistance |
Citations (1)
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US2938875A (en) * | 1956-11-19 | 1960-05-31 | Shell Oil Co | Polyepoxy-substituted aromatic compounds and polymers |
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- 1969-07-17 US US842526A patent/US3635843A/en not_active Expired - Lifetime
Patent Citations (1)
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US2938875A (en) * | 1956-11-19 | 1960-05-31 | Shell Oil Co | Polyepoxy-substituted aromatic compounds and polymers |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4339571A (en) * | 1979-05-08 | 1982-07-13 | Ciba-Geigy Corporation | One-component systems based on crystalline epoxide resins |
EP0018950A1 (en) * | 1979-05-08 | 1980-11-12 | Ciba-Geigy Ag | Crystalline epoxy resin based one component systems and their application |
US4687832A (en) * | 1984-09-20 | 1987-08-18 | Dainippon Ink And Chemicals, Inc. | Novel epoxy resin compositions |
US4786668A (en) * | 1986-06-09 | 1988-11-22 | Shell Oil Company | Resin materials |
US4786669A (en) * | 1986-06-09 | 1988-11-22 | Shell Oil Company | Lightly cross-linked resin materials |
US4707534A (en) * | 1986-12-09 | 1987-11-17 | Minnesota Mining And Manufacturing Company | Glycidylethers of fluorene-containing bisphenols |
AU596241B2 (en) * | 1986-12-09 | 1990-04-26 | Minnesota Mining And Manufacturing Company | Glycidylethers of fluorene-containing bisphenols |
EP0428871A3 (en) * | 1989-11-22 | 1992-04-29 | Sumitomo Bakelite Company Limited | Epoxy resin composition for semiconductor sealing |
EP0428871A2 (en) * | 1989-11-22 | 1991-05-29 | Sumitomo Bakelite Company Limited | Epoxy resin composition for semiconductor sealing |
US5143951A (en) * | 1989-11-22 | 1992-09-01 | Sumitomo Bakelite Company Limited | Epoxy resin composition for semiconductor sealing |
EP0450944A2 (en) * | 1990-04-04 | 1991-10-09 | Toray Industries, Inc. | An epoxy resin composition for encapsulating a semiconductor device |
EP0450944A3 (en) * | 1990-04-04 | 1992-01-15 | Toray Industries, Inc. | An epoxy resin composition for encapsulating a semiconductor device |
US5939472A (en) * | 1994-03-04 | 1999-08-17 | Mitsubishi Denki Kabushiki Kaisha | Epoxy resin composition for molding having improved mechanical properties and crack resistance |
WO1996018669A1 (en) * | 1994-12-16 | 1996-06-20 | Ppg Industries, Inc. | Epoxy-amine barrier coatings with aryloxy or aryloate groups |
US5637365A (en) * | 1994-12-16 | 1997-06-10 | Ppg Industries, Inc. | Epoxy-amine barrier coatings with aryloxy or aryloate groups |
EP0878471A1 (en) * | 1997-05-16 | 1998-11-18 | National Starch and Chemical Investment Holding Corporation | Reactive radiation- or thermally-initiated cationically-curable epoxide monomers and compositions made from those monomers |
EP0878472A1 (en) * | 1997-05-16 | 1998-11-18 | National Starch and Chemical Investment Holding Corporation | Reactive radiation- or thermally- initiated cationically-curable epoxide monomers and compositions made from those monomers |
US5962547A (en) * | 1997-05-16 | 1999-10-05 | Nikolic; Nikola A. | Reactive radiation- or thermally-initiated cationically-curable epoxide monomers and compositions made from those monomers |
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